Process for the preparation of olefins using carbonyl compounds and silyl-substituted organometallic compounds

ABSTRACT

A PROCESS FOR THE CONVERSION OF CARBONYL COMPOUNDS TO THE CORRESPONDING OLEFINS USING TRIALKYLSILY-ORGANOMETIC COMPOUNDS.

United States Patent O Int. Cl. C07c 11/02 US. Cl. 260-677 2 ClaimsABSTRACT OF THE DISCLOSURE A process for the conversion of carbonylcompounds to the corresponding olefins usingtrialkylsilyl-organometallic compounds.

This is a divisional application of my copending application, Ser. No.693,084, filed Dec. 26, 1967, now Pat. No. 3,517,042, June 23, 1970.

OBJECTS OF THE INVENTION An object of this invention is the formation ofolefinic compounds in good yields from a variety of carbonylcontainingcompounds.

A fiurther object of this invention is to prepare compounds useful aschemicals for the prepration of plastics, resins and synthetic rubbers.

A further object of this invention is to prepare olefinic compoundsheretofore difficult to obtain.

BACKGROUND OF THE INVENTION Several methods are known in the prior artfor the conversion of carbonyl compounds to the corresponding methylenederivatives. The most common and most frequently used method for thisconversion has the common feature of employing phosphorus-substitutedcarbanions, the well-known Wittig" reagents, which are phosphorousylids, as the reactive intermediates, see -A. W. Johnson, YlidChemistry, Academic Press, Inc., New York (1966). The phosphinyl-alkylmetal compounds, L. Horner, H. Hoffman, H. G. Wippel, and G. Klahre,Chem. Ber. 92, 2499 (1959), and the phosphonate carbanions, W. S.Wadsworth, Jr., and W. D. Emmons, J. Am. Chem. Soc., 83, 1733 (1961),have also been employed to convert carbonyl compounds to theircorresponding olefins. In addition, the u-lithiophosphosphonic acidbisamides, E. J. Corey and G. T. Kwiatkows'ki, I. Am. Chem. Soc., 88,5652 (1966), and the 0,0-dialkyl-a-lithiophosphonothioate esters, E. J.Corey and G. T. Kwiatkowski, J. Am. Chem. Soc., 88, 5654 (1966), asphosphorous-substituted carbanions also have been used to form olefinsfrom carbonyl compounds. In addition to the organophosphorous compounds,a boron-substituted carbanion, G. Cainelli, G. Dal Bello, G. Zubiani,Tetrahedron Letters, 4315 (1966), a sulfur-substituted carbanion, E. J.Corey and T. Durst, I. Am. Chem. Soc., 88, 5656 (1966), and asilicon-phosphorous-snbstituted carbanion, H. Gilman and R. A. Tomasi,J. Org. Chem., 27, 3647 (1962), have been used to produce olefins fromcarbonyl compounds.

Although the course of the reaction and the products obtained willdepend on the specific carbanion, hereinbefore described, and carbonylcompound used, the formation of olefins by the use of anheteroatom-substituted carbanion can be summarized as follows using thewellknown Wittig reagents as the carbanion R -P-CH; at... wherein R andR are hydrocarbon groups.

SUMMARY OF THE INVENTION The present invention relates, primarily to aprocess consisting of reacting a metalated silane with a carbonylcompound to produce an olefinic compound. The process of the presentinvention is summarized below as:

wherein R R R R R M and X are as hereinafter defined.

The present invention also relates to novel metalated silanes which canbe used in the process of this invention for the preparation of olefiniccompounds.

TH-E SILANES The silanes suitable for the purposes of this invention andwhich are to be metalated with metalating agents, heremafter described,are of the general formula wherein R R and R each are saturated alkylgroups having from 1 to about 20 carbon atoms, wherein X is (1)hydrogen, (2) a halogen, such as bromine, chlorine or iodine, or (3) anelectron-withdrawing group such as phenyl, methylthio,diphenylphosphino, diphenylthiophosphinyl, and trimethylsilyl groups.

Where X is hydrogen the silane described above is atrialkylmethylsilane.

Where X is a halogen such as chlorine, bromine or iodine, the silanedescribed is a trialkyl(halomethyl)silane, e.g., thetrialkyl(chloromethyl)silane, the trialkyl(bromomethy1)silane, and thetrialkyl(iodomethyl)silane; and

Where X is an electron-withdrawing group selected from the groupconsisting of phenyl, methylthio, diphenylphosphino,diphenylthiophosphinyl and trimethylsilyl groups, the silane describedis a trialkyl(substituted-methyl)silane, e.g., thetrialkyl(phenylmethyl)silane, the trialky1(methylthiomethyl)silane, thetrialkyl(diphenylthiophosphinylmethyl)silane, thetrialkyl(diphenylphosphinomethyl)silane, and thetrialkyl(trimethylsilylmethyl)silane.

Suitable R R and R groups on the trialkylmethylsilanes, thetrialkyl(ha1omethyl)silanes and the trial-kyl-(substituted-methyl)silanes and subsequently on the correspondingtrialkylsilylmethylmetals, and the trialkylsilyl- (substituted)methylmetals prepared upon reaction of the silanes with the appropriatemetalating agents, described hereinafter, include straight chain,branched chain and cyclic saturated alkyl groups containing from 1 toabout 20 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl,

n-butyl, Z-methylpropyl, n-pentyl, 2-methy1butyl, isopentyl, n-hexyl,2-methylpentyl, 2,3-dimethylbutyl, 2,2-dimethylbutyl, n-heptyl,2,2-dimethylpentyl, n-octyl, 2,2-dimethylhexyl, isooctyl, 2-ethylhexyl,n-nonyl, n-decyl, tripropylene, n-undecyl, n-dodecyl, tetrapropylene,n-tridecyl, ntetradecyl, n-pentadecyl, n-hexadecyl, n-octadecyl,eicosyl, cyclopentyl, cyclohexyl, cyclooctyl, methylcyclohexyl,

3 2-cyclohexyldodecyl, 12-cyclohexyldodecyl, and dodecylcyclohexyl, saidsilanes having 40 or less carbon atoms and preferably less than 30carbon atoms.

For the trialkylmethylsilane the preferred alkyl group is methyl and thepreferred trialkylmethylsilane is tetramethylsilane; for thetrialkyl(halomethyl)silane the preferred halogen is chlorine, thepreferred alkyl group is methyl, and the preferredtrialkyl(halomethyl)silane is trimethyl(chloromethyl)silane; and for thetrialkyl(substituted-methyl)silane the preferred alkyl group is methyl,the preferred electron-withdrawing groups are the phenyl and themethylthio groups, and the preferred trialkyl-(substituted-methyl)silanes are trimethyl(phenylmethyl) silane andtrimethyl(methylthiomethyl)silane.

METALATING WGENTS The metalating agents, hereinafter described, arereacted with the appropriate silanes to prepare the metalated silanes.Since X, as hereinbefore defined, can be a number of different moieties,the preparation of the metalated silanes will depend on the particularsilane used as the starting material.

The trialkylmethylsilanes are reacted with a metalating agent selectedfrom the group consisting of an alkylsodium, an alkylpotassium and acomplex of an alkyllithium and an alkylenediamine, hereinafterdescribed, to produce the trialkylsilylmethylmetals according to thefollowing:

E (IUR RQSi-(FH MY (RIRQRB) SiCM YH where M=Na, Li or K Y=alkyl group(This method of preparing the trialkylsilylmethylmetals is described inmy copending application, Ser. No. 686,291, filed Nov. 28, 1967.)

Metalating agents which are useful in metalating thetrialkylmethylsilanes are alkylsodiums and alkylpotassiums. Thealkylsodiums and alkylpotassiums which are suitable for use in thisinvention are those wherein the alkyl group is a straight chain orbranched chain group containing from 1 to about 20 carbon atoms. Themetal atom is preferably attached to a primary carbon atom since thecorresponding secondary or tertiary organometallic sodiums andpotassiums are difficult, if not impossible, to prepare.

Suitable alkyl groups for the alkylsodiums and alkylpotassiums aremethyl, ethyl, propyl, butyl, 3-methylbutyl, isopropyl, n-pentyl,isopentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, tetrapropylene4-propyldecyl, n-hexadecyl, n-dodecyl, and eicosyl.

Alkyllithiums are also suitable metalating agents for use in metalatingthe trialkylmethylsilanes. The alkyllithiurns are preferably selected sothat the point of attachment of the lithium is to a primary carbon atom.Alkyllithiums in which the attachment is at a secondary carbon atom canbe used, however, they are less effective than those in which thelithium is attached through a primary carbon atom. Alkyllithiums inwhich the point of attachment is a tertiary carbon atom, e.g.,t-butyllithium, are not effective.

Although it is possible to metalate using alkyllithiums alone, themetalation proceeds very slowly. The reactivity of the alkyllithium isincreased considerably by complexation with a diamine, hereinafterdescribed, in contrast to the situation with the alkylsodium andalkylpotassiurn, since their reactivity toward trialkylmethylsilane isnot significantly altered by complexation with a diamine. The metalatingcomplex of organolithium compounds and diamines is described by G. G.Eberhardt and W. A. Butte, in J. Org. Chem., 29, 2928 (1964) and A. W.Langer, J11, in Trans. NY. Acad. Sci., Ser. II, 27, 741 (1965).

The diamine compound used in the complexation with the alkyllithium toincrease its reactivity is shown as follows:

wherein R R R and R are saturated straight chain, branched chain, orcyclic alkyl groups having from 1 to about 20 carbon atoms. R in theabove generic formula is a saturated alkylene straight chain grouphaving from 1 to about 4 carbon atoms with the total carbon atoms insaid diamine compound being from about 5 to about 30 carbon atoms.Suitable alkyl groups for R R R and R include methyl, ethyl, n-propyl,isopropyl, nbutyl, n-pentyl, isopentyl, n-hexyl, 2,2-dimcthylpentyl,2-methylpentyl, n-octyl, 2,2-dimethylhexyl, isooctyl, 2- ethylhexyl,n-noyl, n-dccyl, tripropylene, n-undecyl, ndodecyl, tetrapropylene,n-tridecyl, ethyldodecyl, 2,5,9- trimethyltridecyl, n-tetradecyl,n-pentadecyl, n-hexadecyl, n-octadecyl, eicosyl, cyclopentyl,cyclohexyl, cyclooctyl, methylcyclohe'xyl, 2-cyclohexyldodecyl,l2-cyclohexyldodecyl and 4-dodecylcyclohcxyl. The R, R R and R alkylgroups can be the same or different. The preferred R R R and R groupsare methyl and ethyl groups.

Suitable R groups include methylene, ethylene, propylene, and butylenegroups. The preferred R group is ethylene with methylene and propylenealso being preferred. Diamines in which the ring size of the resultingcomplex with the alkyllithium involves 5, 6, or 7 atoms are veryeffective complexing agents.

Examples of suitable diamine complexing agents includeN-methyl,N-ethyl,N'-propyl,N butylpropylenediamine, N-dodecyl,N,N',N-trimethylmethylenediamine, N-octyl,N,N,N'triethylbutylenediamine, N,N,N,N'- tetraethylpropylenediamine, andN-eicosyl,N,N,N'-tri methylcthylenediamine.

The preferred diamine complexing agents are N,N,N,N-tetramethylethylenediamine, N,N,N,N tetraethylethylenediamine, N,N,N,Ntetramethylpropylenediamine, and N,N,N',N-tetraethylpropylenediamine.

The ratio of alkyllithium to the diamine for complexation can be from 1to 1 to 4 to 1. The preferred ratio is 1 to 1.

The trialkyl(halomethyl)silanes are reacted with a metalating agentwhich is an alkali metal or an alkaline earth metal such as lithium,sodium, potassium or magnesiurn to produce the trialkylsilylmethylmetalsaccording to the following:

where X =Cl, Br or I M=Li, Na, K or Mg M=Li, Na, K or MgX (This methodof preparing the trialkylsilylmethylmetals Where M is Mg is described inJ. -R. Gould, L. H. Sommer and F. C. Whitmore, J. Am. Chem. Soc., 70,2874 (1948).)

The metalating agents which can be used to react with thetrialkyl(halomethyl)silanes to form the trialkylsilylmethylmetals aremetallic sodium, metallic potassium, metallic lithium and metallicmagnesium. The preferred metalating agent for thetrialkyl(halomethyl)silanes is magnesium metal.

The trialkyl(substituted-methyl)silanes are recated with a metalatingagent which is an alkylor aryl-sodium, an alkylor aryl-potassium, and analkylor aryl-lithium, or a complex of an alkyllithium and analkylenediamine,

hereinbefore described, to produce thetrialkylsilyl(substituted)methylmetals according to the following:

where X is an electron-withdrawing group hereinbefore described M=Na, Kor Li Y=an alkyl group or aryl group [Where X, R R and R are phenyl,this method of preparation is described in H. Gilman and H. Hartzfeld,J. Am. Chem. Soc., 73, 5878 (1951)].

Suitable metalating agents for reaction with thetrialkyl(substituted-methyl)silanes to form the trialkylsilyl(substituted)methylmeta-ls are alkylor aryl-sodiums, potassiums orlithiums, wherein the alkyl or aryl group contains from 1 to about 20carbon atoms, and the complexes of the alkyllithiums and the diamineshereinbefore described. Because of the fact that in the trialkyl(substituted-methyl)silane an electron-withdrawing group is present, agreater variety of alkylor aryl-sodiums, potassiums, and lithiums arereactive towards these silanes. The preference for attachment for thealkali metal to the primary carbon atom is not as great as in thesituation hereinbefore described with the trialkylmethylsilane.

Suitable alkyllithiums, alkylsodiums, and alkylpotassiums for use as themetalating agent are those wherein the alkyl groups are straight chain,branched chain and cyclic containing from 1 to about 20 carbon atoms,e.g., methyl, ethyl, propyl, n-butyl, 3-methylbutyl, isopropyl,n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, ndecyl, tetrapropylene,4-propylundecyl, n-hexadecyl, ndodecyl, eicosyl, cyclohexyl,cyclopentyl, and methylcyclohexyl.

Suitable aryl groups for use in the aryl-sodiums, potassiums andlithiums are the following: phenyl, biphenyl and naphthyl groups and thesubstituted aryl groups such as tolyl, xylyl, and decylphenyl. Aralkylor alkaryl groups such as phenyldecyl, butylphenyl, and4,4-diphenylbutyl are also suitable.

The preferred metalating agents for the trialkyl(substituted-methyl)silanes are n-butyllithium and the complexes of thealkyllithiums with the diamines hereinbefore described as preferred formetalating the trialkylmethylsilanes.

The metalating agents are normally sold commercially with an excess of aliquid saturated hydrocarbon such as pentane, hexane, octane,cyclohexane, isooctane, nonane, or decane. However, any saturatedhydrocarbon having from 5 to 16 carbon atoms and being either straightchain, branched chain or cyclic can be used. The concentration of themetalating agent is usually about 1.5 molar and can range from 1 molarto 3 molar concentration. In addition to the saturated hydrocarbonsolvents, ether solvents such as diethyl ether, dibutyl ether,tetrahydrofuran, dioxane, and 1,2-dimethoxyethane can also be used inthe metalating step. The preferred solvent is hexane because the boilingpoint is optimum and thus it is easily removed by distillation withoutany adverse affects on the metalated silane. Other preferred solventsare pentane and heptane. T etrahydrofuran is also preferred.

The metalation reaction must take place in an inert atmosphere, e.g.,nitrogen, argon, or helium since the organo-metallic compounds arehighly reactive and will be decomposed if exposed to a reactiveatmosphere, such as air or moisture. The preferred inert atmosphere isargon.

The temperature of the reaction can be any temperature at ,which thereaction mixture is liquid, i.e., above about 60 C. The temperature isusually less than about C. since organometallic compounds tend todecompose above this temperature. The preferred temperature is about 20C. (room temperature).

A stoichiometric amount or an excess of the silane in relation to themetalating agent is preferably employed to prevent excess metalatingagent from interfering with the subsequent reaction with carbonylcompounds. If excess metalating agent is present it is readily reactedwith and competes in subsequent reactions with the carbonyl compounds.The silane can even be used as the reaction medium in ratios as high as4:1 with respect to the metalating agent.

Where X, in the trialkyl (substituted-methyl)silanes, is thediphenylthiophosphinyl group, the diphenylphosphino group, thetrimethylsilyl group or the methylthio group, and these silanes aremetalated to form the lithium, sodium or potassium organometallics, theresulting compounds are new classes of compounds. These new classes ofcompounds are specifically thetrialkylsilyl(diphenylthiophosphinyl)methylmetals, thetrialkylsilyl(trimethylsilyl)methylmetals, thetrialkylsilyl(diphenylphosphino) methylmetals and thetrialkylsilyl(methylthio)- methylmetals. All of these compounds areuseful to produce known substituted olefins. For example: wheretrialkylsilyl(diphenylphosphino)methylmetal is reacted withbenzaldehyde, fi-styryldiphenylphosphine,

a known compound [see D. Gloyna and H. H. Henning, angew. Chem.internat. Edit, 5, 847 (1966)] is obtained; Wheretrialkylsilyl(methylthio)methylmetal is reacted with benzaldehyde, CHSCH:CHC H fl-styryl methyl sulfide, a known compound [see M. C. Caserio,R. E. Pratt and R. J. Holland, I. Am. Chem. Soc., 88, 5747 (1966)] isobtained; where trialkylsilyl-(trimethylsilyllmethylmetal is reactedwith benzaldehyde,

(CH3 CHC6H5 B-styryltrimethylsilane, a known compound [see L. H.

Sommer et al., J. Am. Chem. Soc., 76, 1613 (1954)] is obtained. [(R R R)SiCH=CHC H is also formed] CARBONYL CO'MPOUNDS The carbonyl compoundswhich are useful and can be advantageously employed in this inventionare of the following general formula:

II R40 R5 wherein each R and R is selected from the group consisting ofhydrogen and alkyl, aryl, alkaryl, aralkyl, cycloalkyl and, where R istaken together with R bivalent alkylene groups, said groups having from1 to about 30 carbon atoms, said carbonyl compound containing 40 or lesscarbon atoms and preferably less than 30 carbon atoms. Upon reactionwith the carbonyl compound the metalated silanes yield olefins of thefollowing general formula wherein R R and X (except not a halogen atom)are as hereinbefore described.

Where R and R are alkyl groups suitable groups are as follows: methyl,ethyl, n-propyl, isopropyl, npentyl, isopentyl, n-hexyl,2,2-dimethylpentyl, n-heptyl, n-octyl, 2,2-dimethylhexyl, isooctyl,2-ethylhexyl, nnonyl, n-decyl, tripropylene, n-undecyl, n-dodecyl,tetrapropylene, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl,n-octadecyl, eicosyl, cyclopentyl, cyclohexyl, cyclohexylmethyl,methylcyclohexyl, 2-cyclohexyldodecyl, 12- cyclohexyldodecyl,4-dodecylcyclohexyl, and cyclooctyl groups.

Other suitable R and R groups include aryl groups such as phenyl,biphenyl, and naphthyl groups and substituted aryl groups such as tolyl,dodecylphenyl, 2- methyl-4-biphenyl, 4-methyl-1-naphthyl,4-octyl-2-naphthyl, and 2,4-dimethylphenyl groups. Still other examplesof suitable groups for R and R include aralkyl groups such as3-phenyldodecyl, 4-phenyloctyl, 4-phenyldecyl, 4- phenylbutyl,4-tolylmethyl, 3-(2-naphthyl)propyl, 4-(1- naphthyl)butyl,3-biphenylpentyl, and 3-biphenylpropyl groups.

Other substituted R and R groups which are suitable include3-(p-tolyl)propyl, 4-phenylbutyl, 4-(1-naphthyl)- hexyl,3-(ethylnaphthyl)propyl, 3-(4-biphenyl)propyl, 3- (dimethyl)propyl, and3,3-diethylhexyl. Where R and R are taken together, as a bivalentalkylene group, suitable bivalent alkylene groups are ethylene,propylene, butylene, pentalene, octalene, decalene, hexadecalene andeicosalene.

Phenyl and methyl are preferred as the R and R groups. Also preferredare alkyl groups having from 1 to 8 carbon atoms in each R and R group.

The reaction of the metalated silane with the carbonyl compound iscarried out in an inert atmosphere such as argon, although nitrogen andhelium are also suitable and preferred. The reaction is normallyconducted in a solvent medium and at a temperature of from about -60 C.to about 100 C. The preferred temperature is about C. (roomtemperature). Suitable solvent mediums are saturated hydrocarbons havingfrom about 5 to 16 carbon atoms such as pentane, hexane, heptane,octane, isooctane, cyclopentane, cyclohexane, and cycloheptane andaromatic hydrocarbons such as benzene, toluene, and xylene. Ethersolvents such as tetrahydrofuran, dioxane, 1,2-dimethoxyethane, dibutylether and diethyl ether are also suitable for the purpose of thisinvention as solvents. Ether solvents such as tetrahydrofuran arepreferred.

In some cases on reaction of the carbonyl compound with the metalatedsilane a relatively stable metal alkoxide is formed. For example, themagnesium (Grignard) entity, (R R R )SiCH MgX, forms a magnesiumalkoxide, which on acidification with dilute ammonium chloride yieldsthe (B-hydroxyalkyl trialkylsilane. The B-hydroxyalkyl trialkylsilane isconverted to the corresponding olefin by reaction with sodium orpotassium hydride or potassiumt-butoxide. The conversion of the(fl-hydroxyalkyD-trialkylsilane to the sodium, potassium, or butoxideintermediate to form the olefin is preferred in some cases because ofkinetic considerations, i.e., where the decomposition of the alkoxideinto the olefin is slow.

In the reaction of the trialkylsilyl organometallic with a carbonylcompound, the following well-known compounds are produced:

(a) where benzophenone is reacted with a trialkylsilylmethylmetalstyrene is produced, which is a well-known monomer useful in themanufacture of plastics, synthetic rubbers and resins;

(b) where octanal is reacted with a trialkylsilylmethylmetal l-nonene isproduced, which is useful in organic synthesis, as a wetting agent andas a lubricating oil additive, see Elizabeth and Arthur Rose, CondensedChemical Dictionary, 7th ed., p. 677, Reinhold, New York, 1966;

(c) where acetone is reacted with a trialkylsilylmethylmetal,isobutylene is produced and the isobutylene is useful in the productionof isooctane, butyl rubber, polyisobutene resins and copolymer resinswith butadiene and acrylonitrile, see Condensed Chemical Dictionary, op.cit. supra, p. 518.

Other compounds produced by utilizing this invention are known compoundsas shown by the cited references,

(a) the reaction of benzophcnone with a trialkylsilylhenyl)methylmetalproduces triphenylethylene, see

8 Heilbron, Dictionary of Organic Compounds, vol. 5, p. 3199, OxfordUniversity Press, 1965;

(b) the reaction of acetone with a trialkylsilyl(phenyl) methylmetalproduces [3,f3-dimethylstyrene, see Heilbron, vol. 4, p. 2300, op. cit.supra;

(c) the reaction of benzophenone with a trialkylsilylmethylmetalproduces 1,1-diphenylethy1ene, see The Merck Index of Chemicals andDrugs, 7th ed., p. 381, Merck & Co., Rahway, N.J., 1960;

(d) the reaction of a trialkylsilyl(trimethylsilyl)methylmetal withbenzaldehyde produces ,B-styryltrimethylislane, see E. A. Chemphev andN. G. Tolstikova, Isv. Akad. Nauk SSSR, Otd. Khim. Nauk, pp. 1223-8,(1962) [C.A., 58, 5712h (1963)];

(e) the reaction of a trialkylsilyl(diphenylphosphino)- methylmetal withbenzaldehyde produces B-styryldiphenyl hosphine. see H. Hoffmann and H.J. Diehr, Chem. Ber., 98, 363-8 (1965);

(f) the reaction of a trialkylsilyl(methylthio)methylmetal withbenzaldehyde produces fl-styryl methyl sulfide, see G. Wittig and M.Schlosser, Chem. Ber., 94, 1373-83 (1961);

(g) the reaction of a trialkylsilyl(phenyl)methylmetal withcyclohexanone produces cyclohexylidenephenylmethane, see S. Trippett andD. M. Walker, J. Chem. Soc., 1266, (1961).

As can be seen by the above, compounds produced by the process of thisinvention are useful in many waysparticularly in the synthesis ofpolymeric materials useful as plastics, resins and synthetic rubbers.

All parts, percentages and ratios herein are by weight unless otherwisespecified. The following examples are illustrative of the invention andshould not be taken as limiting the scope of the claims.

EXAMPLES GENERAL All reactions and procedures hereinafter described wereperformed in an atmosphere of oxygen-free argon. The nmr spectra wereobtained on Varian Associates I-IR- (phosphorus) and HA- (proton)spectrometers. The infrared spectra were obtained on a Perkin-ElmerInfracord spectrometer. The gas-liquid phase chromatography was done onan Aerograph instrument using a SE-30 column on Chromosorb W. The massspectrographic analyses were obtained on an Atlas CH-4 massspectrometer.

The following example, given generically, sets forth the procedurefollowed in the examples referred to in the tables which are to followhereafter. The tables which follow each step refer to the step of theprocedure which preceeds it, e.g., the metalated silanes prepared instep (a) are summarized in Table I immediately following step (a) andthe olefins prepared in step (b), by reaction of the metalated silaneswith the carbonyl compounds, are summarized in the Table II immediatelyfollowing step (b). The two tables are co-ordinated through thecorrespondence of the example numbers, e.g., Example 1 in Table I, step(a) continues as Example I in Table II step (b).

(a) Preparation of metalated silanes (1) Halomethylsilanes: 0.05 mole ofthe trialkyl(halomethyl)silane in 50 ml. of hexane was added dropwise to0.1 g. at. wt. of an alkali metal (e.g., sodium, lithium, or potassium)dispersed in 50 ml. of hexane or of magnesium ribbon suspended in 50 ml.of tetrahydrofuran undeer a blanket of argon. The unreacted metal wasfiltered off subsequently.

(2) Methylsilanes: 0.05 mole of the trialkylmethylsilane in 50 ml. ofhexane was added to 0.05 mole of (1) an alkylsodium, (2) analkylpotassium, or (3) a complex of an alkyllithium and an N,N,N',N'tetraalkylenediamine, prepared by mixing equal molar amounts (0.05 mole)of the alkyllithium and the diamine. The reaction was stirred for threedays at room temperature.

(3) (Substituted-methyl)silanes: 0.05 mole of trialkyl(substituted-methyl)silane in 50 ml. of hexane was added dropwise to0.05 mole of (1) an alkylor aryl-sodium (2) an alkylor aryl-potassium(3) an alkyl-- or aryllithium, or (4) a complex of an alkyllithium andan N,N,N,N' tetraalkylalkylenediamine prepared as in sub-step (2) ofstep (a) above and subsequently stirred for 1 to 4 hours.

The trialkylsilylmethylmetals, as prepared in sub-steps (1) or (2) aboveof step (a) above, the trialkylsilyl- (substituted)methylmetals, asprepared in sub-step (3) of step (a) above, or thetrialkylsilylmethylmagnesium halide (Grignard), as prepared in sub-step(1) of step (a) above, were analyzed either using H nmr spectroscopy, pspectroscop or IR spectroscopy or, in some cases they were deuteratedand then analyzed using a mass spectrograph, to confirm the presence ofthe metalated silane.

When in step (a) above, other trialkylmethylsilanes are substituted forthe tetramethylsilane of Example 15,

TABLE I, Step (Mr-PREPARATION OF THE METALATED SILANE Metalated silanepreparation Example Silano Metalating agent method Metalated silaneformed 1 (CH3)3S1CH2C1 Mg Sub-step (1) (CHs)ss iCH2MgC1 2 (CHmSiCIbCl Mg.....(10 H3)sS1CH2MgCl 3 (CH3)3SiCI-I2Cl Mg (CH3)3Sl CH2l\/Ig0l 4(CHQaSiCHgCl Mg (CH3)3S1CHzMgCl 5.-. (CHsJaSiCHzCl Mg (OH3)3S1CH2M Cl 6(CH3)3SlCH2CflH5 n-C4HqL -TMEDA 1 (CH3) S iCH(C@H )(L i) 7(CHahSiCHzCaHs Il-OiHoLl-TMEDA. (CH'DaSlCH (CaH5) (L1) 8 (CH3)3SiCH2CaH5n-Cifi Li-TMEDA (CH3)3SlCH(CflH5) 9--. (CH3)sSiCHzCaH n-CiHnLi-TMEDA t.H3)3SiCH( BH5) (Li) 10 Ha)aSiCH2P 6115): nhflo i Ha)aS iCH[ (C 5H5)2l(Li) 11 (CH SiCHzP (CnHm n-(liH Li (CHaJaSiCEHP (C H (L1) 12.-(CHa)3SiCH2P (S) (C0115): D- iHO ---d Hs)aS}CH[P (S) (011K921 (L1) 13(OHahSiCHzSCHs 11-C4HnL1 do (CHs)sS CH(SCHa)(L i) 14 (CH3)3SiCH2SCH3n-CqHsL -.d0---.. (CH3)3S1CH(SQH3)(L1) 15 (CH3)3SiCH3 Il-C4H9Ll-TMEDASub-step (2) (CH3)3S1CH L1 1 N,N,N,N-tetramethylethylenediamine.

When in step (a) of Examples 1-5 above other trialkyl(halomethyl)silanesare substituted on a molar basis for the trimethyl(chloromethyl)silaneor when sodium, potassium, or lithium is substituted on an equivalentbasis for the magnesium as the metalating agent, substantiallyequivalent results are obtained in that the correspondingtrialkylsilylmethylmetals are obtained, e.g.,trimethylsilylmethyllithium, triethylsilylmethylpotassium,ethyldimethylsilylmethylsodium, (2,2dimethyl)-hexyldimethylsilylmethyllithium, tributylsilylmethylpotassium,cyclohexyldimethylsilylmethylpotassium, anddodecyldimethylsilylmethylsodium.

When in step (a) other trialkyl(substituted-methyl) silanes aresubstituted on a molar basis for the trimethyl (phenylmethyl)silane ofExamples 6-9, for the trimethyl (diphenylphosphinomethyl)silane ofExamples 10-11, for the trimethyl(diphenylthiophosphinylmethyl)silane ofExample 12, or for the trimethyl(methylthiomethyl)silane of Examples 13and 14; or when other metalating agents such as alkylor aryl-sodiums,potassiums, or lithiums are substituted on a molar basis for themetalating agents used, i.e., for the n-C H Li-TMEDA complex in Examples6-9 or for the n-C H Li in Examples 1014, e.g., methyl, ethyl, propyl,n-butyl, n-pentyl, n-decyl, n-dodecyl, eicosyl, phenyl, tolyl andnaphthyl sodiums, potassiums and lithiums, or when other complexes ofalkyllithiums with N,N,N',N'- tetraalkylalkylenediamines are substitutedon a molar basis for the n-butyllithium-TMEDA complex, e.g., thecomplexes of methyl, ethyl, propyl, n-pentyl, n-octyl, n-decyl,n-hexadecyl and eicosyl lithiums withN-methyl,N-ethyl,N'-propyl,N'-butylpropylenediamine,N-dodecyl,N,N,N'-trimethylmethylenediamine,N-octyl,N,N',N'-triethylbutylenediamine,N,N,N',N-tetraethylpropylenediamine, orN-eicosyl,N,N,N'-trimethylethylenediamine,

substantially equivalent results are obtained in that the correspondingtrialkylsilyl (substituted)methylrnetals are obtained,

e.g., triethylmethylsilane, ethylbutyldimethylsilane,dodecyltrimethylsilane, eicosyldipropylmethylsilane,cyclohexyldodecyldimethyl silane, (2,2 dimethylbutyl)trimethylsilane(cyclohexyl)decyldibutylmethylsilane; or other metalating agents such asalkyl-sodiums or potassiums are substituted on an equivalent basis forthe n- C H LiTMEDA complex, e.g., methyl, ethyl, propyl, n-butyl,n-pentyl, n-decyl, n-dodecyl, eicosyl, phenyl, tolyl and naphthylsodiums, potassiums and lithiums, or other complexes of alkyllithiumswith N,N,N',N-tetraalkylalkylenediamines substituted on a molar basisfor the n-C H Li-TMEDA complex, e.g., the complexes of methyl, ethyl,propyl, n-pentyl, n-octyl, n-decyl, n-hexadecyl and eicosyl lithiumswith N-methyl,N-ethyl,N'- propyl,N' butylpropylenediamine, Ndodecyl,N,N',N'- thimethylmethylenediamine, N octyl,N,N',N'triethylbutylenediamine, N,N,N',N'-tetraethylpropylenediamine, and Neicosyl,N,N,N trimethylethylenediamine, substantially equivalent resultsare obtained in that the corresponding trialkylsilylmethylmetals areobtained.

When in step (a) above, other solvents such as saturated hydrocarbonsare substituted for the hexane or ether solvents are substituted for thetetrahydrofuran, either wholly or in part (e.g., 1:1 mixtures),substantially equivalent results are obtained in that the metalatedsilanes are prepared, e.g., hydrocarbon solvents such as: pentane,octane, isooctane, nonane, decane, isododecane, and cyclohexane for thehexane and ether solvents such as dimethyl ether, dibutyl ether,dioxane, and 1,2-dimethoxyethane for the tetrahydrofuran.

(b) Reaction of the metalated silane with the carbonyl compound Thefollowing generic procedure was used in step (b) summarized in Table IIhereinafter. The reaction mixture containing the metalated silane (referto Table I, Examplesl-IS for more specificity) as prepared in step (a)above, was added dropwise and with stirring to an equivalent amount(0.05 mole) of the carbonyl compound,

see Table II hereinafter, dissolved in 50 ml. of tetrahydrofuran. Themixture was stirred for 30 minutes to 24 hours. The temperature wasmaintained below the reflux temeprature by means of a water bath. On aworkup, the olefin formed [(R )(R )C=CHX, wherein R R and X are ashereinbefore described except that X is not a halogen atom], wasanalyzed and its structure confirmed using either H nmr, P nmr, IRspectroscopy or gas-liquid phase chromatography.

(c) Conversion of the magnesium alkoxide to the olefin Where themetalated silane was the magnesium (Grignard) reagent, (Examples 1-5)prepared as in sub-step (1) of step (a) above, and was subsequentlyreacted with a carbonyl compound.

TABLE II, Step (b).REACTION OF THE METALATED SILANE WITH THE CARBONYLCOMPOUND Carbonyl step (0) Yield, Method of analysis Ex. compoundIntermediate isolated Base used Olefin isolated 1 percent (see keybelow) 1 0 (CHa)aSiCHz(OH) (CaHsM KH (CtHs)2C=CH2 86 (1), (3), (4)

ca a o s 2 (CHa)aSlCH2C(OH)(CaHu)1 NaH (CaHis)2C=CHn 67 (1), (3), (4)

CaH5( 3Co s 3 0 (CH:)3S1CH2C (H) (OH) (00115) KH Polystyrene 91 (3), (4)

CeH H 4 O (CH3)3S1CH2C(H) (OH) (Il-C7H15) KH I1-C7HisCH=CH2 70 (1), (3),(4)

n-C H L H 5 (CH3)3S1CH2C (OH) (CH3): t-CrHnOK (CHa)2C=CHz (3) CH tiOH;

6 0 None N0ne-.-....... (CaH5)2C=C1I(COHs) 77 (l), (3), (4)

CeIIa Cu s 7 do "do (C3115) CH=CH(C3H5) 72 (3), (4)

CaHa H 8 0 ..do ..do (CaHa)CH=C(CHa)z (1), (3), (4)

Cli CH;

9 C-C5H1QC=() -(10 .410 CC5HlnC=CH(C0lI5) 5 (l), (3)

.....do ..d0 [(05115) 2P]CH=CH(C0H5) 53 (1), (2), (3), (4)

. do d0 [(CaH5)zP]CH=C(Calls): (1), (2), (3), (4)

CtHs Ce s 12 0 ..do ..do (CoHa)2P(S) CH=C(C5H5)2 (1), (2), (3), (4)

CtHs Co n 13 do .do CHaSCH=CHCaH5 64 (1), (3), (4)

CuHs H 14 do do CH SCH=C(CII5): 56 '(l), (3), (4)

C H t l C311 15 O (CH S1CH;C (OI-I) (CH3): KH (CH )1C=CI-I; 25 (1) 0 ECH 1 Where stereoismnen'sm is possible, 1:1 ratios of eis to transobtained. 6 C, 79.4; H, 5.5. 7 Polymerized on workup. C, 79.8; H, 6.3;S, 14.3.

3 Plus conversion to dibromide. C, 85.4; 11,5.9.

Norm-(1) II llllll. (2) P nmr. (3) 1R. (4) glpc.

When in step (b) above, other carbonyl compounds, e.g., formaldehyde,acetaldehyde, acetone, butanone, phenylmethylketone, propanal, octanal,butanal, p-methylbenzaldehyde, cyclohexanone, naphthaldehyde, dodecanal,pentanone, heptanone, 2,2-dimethyldodecanone, hexadecanal, eicosanone,naphthylethylketone, pentanal, cyclopentanone, cyclooctylphenylketone,(2-phenyl)-ethanal and decanone, are substituted on a molar basis forthe carbonyls used in Examples 1-15, substantially equivalent resultsare obtained in that the corresponding olefins are obtained.

When in step (b) above, other solvents are substituted, either wholly orin part, e.g., 1:1 mixtures, for the tetrahydrofuran substantiallyequivalent results are obtained, e.g., dioxane, 1,2-dimethoxyethane,diethyl ether and dibutyl ether.

What is claimed is:

1. A process for the production of olefinic compounds consisting of thestep of reacting (a) a metalated silane of the general formula wherein RR and R each are saturated alkyl groups having from 1 to 20 carbonatoms, said metalated silane containing 40 carbon atoms or less, andwherein M is selected from the group consisting of Li, Na, K and MgCl,MgBr and MgI, with (b) a carbonyl compound of the following generalformula wherein each R and R is selected from the group consisting ofhydrogen and alkyl, aryl, alkaryl, aralkyl, and cyclic groups, and,Where R is taken together with R bivalent alkylene groups, said groupshaving from 1 to about 30 carbon atoms, said carbonyl compoundcontaining carbon atoms or less, said reaction taking place in an inertatmosphere at a temperature of from about C. to about C. in an inertsolvent.

2. The process of claim 1 wherein R R and R each are short chain alkylgroups having from 1 to 5 carbon atoms, and wherein R and R each arealkyl groups having from 1 to 12 carbon atoms or aryl groups having from6 to 12 carbon atoms.

References Cited UNITED STATES PATENTS 6/1970 Peterson 260-4482 OTHERREFERENCES DELBERT E. GANTZ, Primary Examiner I. M. NELSON, AssistantExaminer US. Cl. X.R. 260-448.Z

22x50 TE Patent Noe 3,657,373

Inventofls) Donald JG Peterson It. is certified that error appears inthe above-identified patent and that said Letters Patent are herebycorrected as shown below:

Column 1, line 34, "prepration" should read --preparation-. Column 4,line 15, "n-noyl should read --=-n-nonyl--, Column 4 line 51, that partof the formula that reads (R R R )SiCM'" should read -=--(R R R )SiCM-nColumn 6, line 29, H. H. Henning" should read ---H'., G Henning-.

Column 7, line 75, "phenyl)methylmetal" should .read --(phenyl)--methylmetala j Column 8, line 12, "islane should read --'-silane-, 7Column 8, end of line 71, "N,N,N' ,N-tetra-*" should read --N,N,N ,Ntetraalkyl I Column 9, Table I, Example 8, under the column headedMetalated silane formed, (CH S-iCH (C I-I )L i) should read ---(CH SiCH(Li)"'" Column 10, line 39, after the first "methylsilane" should readColumn 10, line 51, "thimethylme-th'y-lenediamine" should read--trimethylmethylenediamine Column 11, line 14, "temeprature" shouldread -temperature-. Column 11, Table II, Example 1, under the columnheaded Intermediatisolated, (CH SiCH (OH) (C H should read ""(CH3) 3SiCH C (OH) (CGHS) 2"- q v Column 12, line 2 after "compound" delete thef and insert Column 12, line 16, "algali should read -alkali-.,

Signed and sealed this 19th day of September 1972 (SEAL) Ill twat?EDWARD M@FLETCHER,JR@ 7 ROBERT GO'I'TSCHALK Attestlng OfficerCommissioner of Patents

